Abstract A stereocontrolled synthesis of all-cis-1, 2, 4, 5-tetrafluoro-3-phenylcyclohexane is developed as the first functionalised example of this polar cyclohexane motif. The dipolar nature of the ring, arising due to two 1, 3-diaxial C [BOND] F bonds, is revealed in the solid- state (X-ray) structure. The orthogonal conformation of the aryl and cyclohexyl rings in all-cis- 1, 2, 4, 5-tetrafluoro-3-phenylcyclohexane, and in an ortho-nitro derivative, result in ...